U.S. patent application number 15/506159 was filed with the patent office on 2017-09-07 for composition and method for fighting phytopathogenic fungi.
The applicant listed for this patent is Hochschule Anhalt. Invention is credited to Helmut BALTRUSCHAT, Kathrin KABRODT, Ingo SCHELLENBERG.
Application Number | 20170251668 15/506159 |
Document ID | / |
Family ID | 54292547 |
Filed Date | 2017-09-07 |
United States Patent
Application |
20170251668 |
Kind Code |
A1 |
BALTRUSCHAT; Helmut ; et
al. |
September 7, 2017 |
Composition and Method for Fighting Phytopathogenic Fungi
Abstract
A composition of active ingredients for fighting plant diseases,
composed of at least two different active ingredients, selected
from the group of stilbenes and/or derivatives thereof on the one
hand and of the group of galloylated flavan-3-ols and/or
derivatives thereof, and/or of the group of proanthocyanidins
and/or derivatives thereof on the other hand. As an alternative,
the at least two different active ingredients can be selected from
the group of galloylated flavan-3-ols and/or derivatives thereof
and/or from the group of proanthocyanidins and/or derivatives
thereof. The novel mixtures have a higher effect than the
individual components, there is a synergistic effect. The invention
further relates to a method for fighting fungal plant diseases
using the aforementioned active ingredients.
Inventors: |
BALTRUSCHAT; Helmut;
(Ziemendorf, DE) ; KABRODT; Kathrin; (Bernburg,
DE) ; SCHELLENBERG; Ingo; (Dessau-Rosslau,
DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Hochschule Anhalt |
Koethen |
|
DE |
|
|
Family ID: |
54292547 |
Appl. No.: |
15/506159 |
Filed: |
September 3, 2015 |
PCT Filed: |
September 3, 2015 |
PCT NO: |
PCT/DE2015/000443 |
371 Date: |
February 23, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A01N 31/16 20130101;
A01N 43/16 20130101; A01N 43/16 20130101; A01N 43/12 20130101; A01N
43/90 20130101; A01N 31/16 20130101; A01N 43/12 20130101; A01N
43/90 20130101; A01N 31/16 20130101; A01N 43/16 20130101 |
International
Class: |
A01N 43/16 20060101
A01N043/16 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 4, 2014 |
DE |
10 2014 013 302.8 |
Claims
1. An active ingredient composition for fighting plant diseases,
comprising: at least two different active ingredients selected from
the group of stilbenes and/or their derivatives, and from the group
of galloylated flavan-3-ols and/or their derivatives and/or from
the group of the porathocyanidins and/or their derivatives.
2. An active ingredient composition for fighting plant diseases,
comprising: at least two different active ingredients selected from
the group of the galloylated flavan-3-ols and/or their derivatives
and/or from the group of proanthocyanidins and/or their
derivatives.
3. The active ingredient composition according to claim 1, wherein
the at least two different active ingredients are intermixed in a
ratio from 1:1 to 1:8.
4. The active ingredient composition according to claim 1, wherein
the at least two different galloylated flavan-3-ols are
epigallocatechin gallate and gallocatechin.
5. The active Active ingredient formulation comprised of a
ready-to-use solution, an emulsifiable concentrate, an emulsion, a
suspension, a spray powder, a soluble powder and/or a granulate of
an active ingredient composition according to claim 1, and
additional additives in form of adjuvants.
6. The active ingredient formulation according to claim 5, wherein
the concentration of active ingredients in the active ingredient
formulation is between 4 and 2000 ppm.
7. A method of using an active ingredient composition according to
claim 1, wherein the phytopathogenic fungi to be attacked include
one or more phytopathogenic fungi.
8. A method of fighting fungal plant diseases, comprising the steps
of selecting at least two different active ingredients from the
group consisting of stilbenes and/or derivatives thereof, and, from
the group of galloylated flavan-3-ols and/or derivatives thereof
and/or from the group of porathocyanidine and/or its derivatives,
applying on a plant to be treated simultaneously, jointly,
separately, or sequentially, as such or in their formulations.
9. A method of fighting fungal plant diseases, comprising the steps
of selecting at least two different active ingredients selected
from the group of galloylated flavan-3-ols and/or derivatives
thereof and/or from the group of proanthocyanidins and/or
derivatives thereof, applying on a plant to be treated
simultaneously, jointly or separately, or in succession as such or
in their formulations.
10. The method of claim 8, wherein the active ingredients or their
formulations are also applied as a mixture, simultaneously, before
or afterwards, with additional fungicides, bactericides,
acaricides, nematicides, insecticides and/or further additional
ingredients including herbicides, and/or with fertilizers and/or
growth regulators.
11. The method according to claim 8, wherein the active ingredients
are applied at a concentration in between 4 and 2000 ppm.
12. The active ingredient composition according to claim 3, wherein
the at least two different active ingredients are intermixed in a
ratio from 1:1 to 1:4,
13. The active ingredient composition according to claim 3, wherein
the at least two different active ingredients are intermixed in a
ratio from 1:1 to 1:2.
14. The active ingredient formulation according to claim 5, wherein
the concentration of active ingredients in the active ingredient
formulation is between 8 and 500 ppm.
15. The method according to claim 8, wherein the active ingredients
are applied at a concentration in between 8 and 500 ppm.
16. The active ingredient composition according to claim 2, wherein
the at least two different active ingredients are intermixed in a
ratio from 1:1 to 1:8.
17. The active ingredient composition according to claim 1, wherein
the at least two different galloylated flavan-3-ols are
epigallocatechin gallate and gallocatechin.
18. The active ingredient composition according to claim 2, wherein
the at least two different active ingredients are intermixed in a
ratio from 1:1 to 1:4.
19. The active ingredient composition according to claim 2, wherein
the at least two different active ingredients are intermixed in a
ratio from 1:1 to 1:2.
Description
[0001] The invention relates to an active ingredient composition
for fighting plant diseases. This active ingredient composition is
a fungicidal mixture of compounds in a synergistically effective
amount. The invention further relates to an active ingredient
formulation and to the use of the active ingredient composition or
the active ingredient formulation for fighting fungal plant
diseases. In addition, the invention relates to a method for
fighting fungal plant diseases.
[0002] Compounds from the group of flavan-3-ols and stilbenes and
their efficacy against harmful fungi are fundamentally known from
the literature, for example from Caruso et al. (2011) "Antifungal
Activity of Resveratrol against Botrytis cinerea Is Improved Using
2-Furyl Derivatives" PLoS ONE 6
(10):e25421.doi:10.1371/journal.pone.0025421; Albert et al. (2011)
"Synthesis and antimicrobial activity of (E) stilbene derivatives",
Bioorganic & Medicinal Chemistry, 19 (2011) 5155-5166; Seppanen
et al. (2004) "Antifungal activity of stilbenes in in vitro
bioassays and transgenic Populus expressing a gene encoding
pinosylvin synthase", Plant Cell Reports 22:584-593; and M. Wilmot:
"Inhibition of Phytopathogenic Fungi on Selected Vegetable Crops by
Catechins, Caffeine, Theanine and Extracts of Camellia sinensis
(L.) O. Kuntze", Master Thesis, Faculty of Natural and Agricultural
Sciences, University of Pretoria, September 2006 (Sep. 1, 2006),
pages 1 to 132.
[0003] The present invention is based on the object to achieve an
improved efficacy against harmful fungi while applying a smaller
quantity of active ingredients.
[0004] The object is attained with an active ingredient composition
having the features according to independent claim 1 or claim 2.
Further embodiments are recited in the dependent claims.
[0005] With the aim of reducing the application rates and improving
the activity spectrum of known compounds, for example galloylated
flavan-3-ols and stilbenes, the present invention is based on
synergistic mixtures which have an improved efficacy against
harmful fungi while the total amount of active ingredients applied
is reduced.
[0006] In addition to the mixtures defined at the outset, it has
also been found that harmful fungi can be treated more effectively
when the compounds are applied simultaneously, either in
combination or separately, or when the compounds are applied
consecutively, than when the individual compounds are applied
alone.
[0007] The mixtures of galloylated flavan-3-ols and stilbenes or
their derivatives, when applied simultaneously, either together or
separately, are distinguished by excellent efficacy against a broad
spectrum of plant pathogenic fungi, in particular from the class of
the ascomycetes, basidiomycetes, phycomycetes and
deuteromycetes.
[0008] An active ingredient composition according to the invention
for fighting plant diseases is composed of at least two different
active ingredients selected, on the one hand, from the group of
stilbenes and/or their derivatives, and on the one hand from the
group of galloylated flavan-3-ols and/or their derivatives and/or
from the group of proanthocyanidins and/or their derivatives.
[0009] An alternative active ingredient composition according to
the invention for fighting plant diseases is composed of at least
two different active ingredients selected from the group of the
galloylated flavan-3-ols and/or their derivatives and/or from the
group of proanthocyanidins and/or their derivatives.
[0010] In the context of the present invention, the term
"derivatives" refers to compounds which are formed by modification
reactions such as esterifications, alkylations, aldol reactions,
cycloadditions, decarboxylations, oxidations/reductions,
hydroxylations, cyclizations, methylations, acylations,
galloylations, glycolysis reactions, polymerizations of the
abovementioned compounds.
[0011] The at least two different active ingredients are
advantageously mixed together in a ratio from 1:1 to 1:8,
preferably in a range from 1:1 to 1:4, particularly preferably in a
range from 1:1 to 1:2, including the limiting ratios. The order of
the listed compounds is not defined here, meaning that the range
for the ratio could accordingly also be described by 8:1, 4:1 or
2:1 to 1:1, respectively, when the compound with the larger
proportion is mentioned first. Within the context of the brief
description of the present invention and the claims, the first
number always refers to the active ingredient with the smaller
proportion and the latter number to the active ingredient with the
larger proportion in the active ingredient composition when
indicating the preferred ranges for the ratios between the active
ingredients, irrespective of which of the active ingredients each
forms the smaller or the larger proportion.
[0012] In one embodiment of the invention, the active ingredient
composition is composed of at least two different flavan-3-ols or
their derivatives. A combination of the two different flavan-3-ols
epigallocatechin gallate and gallocatechin has proven to be
particularly advantageous.
[0013] In another embodiment of the invention, the active
ingredient composition is composed of, on the one hand, at least
one flavan-3-ol or a derivative of a flavan-3-ol and, on the other
hand, at least one stilbene or a derivative of a stilbene. Such a
mixture may consist, for example, of epigallocatechingallate and
resveratrol (trans-3,5,4'-trihydroxystilbene),
[0014] Another particularly advantageous active ingredient
composition is composed of at least one proanthocyanidin or a
derivative of a proanthocyanidine and at least one stilbene or a
derivative of a stilbene. An example of such a composition is a
mixture of procyanidine B2 and rhaponticin.
[0015] Another advantageous active ingredient composition is
composed of at least two different stilbenes or their
derivatives.
[0016] When using the active ingredient combination according to
the invention, the application rates can be varied over a
relatively wide range depending on the type of application. In the
treatment of plant parts, the application rates of active
ingredient combinations are generally between 0.1 and 10,000 g/ha,
preferably between 10 and 1000 g/ha (g/ha=grams per hectare).
[0017] The active ingredient combination contained in the
composition can be applied as such, in the form of its formulations
or the applications prepared therefrom, such as ready-to-use
solutions, emulsifiable concentrates, emulsions, suspensions, spray
powders, soluble powders and granules. Another aspect of the
present invention therefore relates to an active ingredient
formulation consisting of a ready-to-use solution, an emulsifiable
concentrate, an emulsion, a suspension, a spray powder, a soluble
powder and/or a granulate of the abovementioned active ingredient
composition and optionally additional additives, in particular
adjuvants. The concentration of the active ingredients in the
active ingredient formulation is generally between 4 and 2000 ppm,
preferably between 8 and 500 ppm.
[0018] Preferably water, optionally with admixtures of additional
solvents, for example ethanol, is used as a solvent.
[0019] The abovementioned active ingredient composition or the
abovementioned active ingredient formulation can be used for
fighting fungal plant diseases, with the phytopathogenic fungi to
be attacked including one or more phytopathogenic fungi.
[0020] Another aspect of the invention relates to a method for
fighting fungal plant diseases wherein at least two different
active ingredients selected, on the one hand, from the group of
stilbenes and/or their derivatives and/or on the other hand, from
the group of the galloylated flavan-3-ols and/or their derivatives
and/or from the group of the proanthocyanidins and/or their
derivatives, are applied on a plant to be treated either
simultaneously, i.e. together or separately, or consecutively as
such or in their formulations. Alternatively, the at least two
different active ingredients are selected from the group of the
galloylated flavan-3-ols and/or their derivatives and/or from the
group of proanthocyanidins and/or their derivatives. The sequential
order in a separate application has generally no effect on the
success of the control. If pathogenic harmful fungi in plants are
to be attacked, for example, a first compound I and a second
compound II are applied separately or jointly, or the soil is
treated before or after seeding of the plants or before or after
the plants emerge. The fungicidal synergistic mixtures according to
the invention, for example from compound I and compound II, may
advantageously be processed in the form of directly sprayable
solutions, powders and suspensions or in the form of highly
concentrated aqueous, oily or other suspensions, dispersions,
emulsions, oil dispersions, pastes, dusts, granules and can be
applied by spraying, misting, dusting, scattering or pouring. The
form of application depends on the intended use, but should in any
event ensure the finest and most uniform distribution of the
mixture according to the invention.
[0021] The formulations are prepared in a conventional manner, for
example by adding solvents and/or carrier substances. Typically,
inert additives such as emulsifiers or dispersants are admixed to
the formulations.
[0022] Suitable surface-active ingredients are alkaline metal
salts, alkaline earth metal salts, ammonium salts of aromatic
sulfonic acids, for example lignin acid, phenolic acid, naphthalene
acid and dibutylnaphthalenesulfonic acid, as well as fatty acids,
alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fatty
alcohol sulfates, and salts of sulfated hexadecanol, heptadecanol
and octadecanol, or of fatty alcohol glycolethers, condensation
products of sulfonated naphthalenes or of naphthalenesulfonic acids
with phenol and formaldehyde, polyoxyethylene octyphenol ethers,
ethoxylated isooctylphenol, octylphenol or nonylphenol,
alkylphenol- or tributylphenylpolyglycol ethers, alkylaryl
polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene
oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl
ethers or polyoxypropylene, lauryl alcohol polyglycol ether
acetate, sorbitan esters, lignin sulfite waste solutions or
methylcellulose.
[0023] Powders, scattering agents and dusting agents can be
prepared by mixing or jointly grinding the compounds I or II or a
mixture of the compounds I and II with a solid carrier. Granules,
for example coating, impregnating or homogeneous granules, are
usually prepared by binding the active ingredient or the active
ingredients to a solid carrier.
[0024] Examples of fillers or solid carriers, respectively, are for
example mineral deposits such as silica gel, silica, silica gel,
silicates, talc, kaolin, limestone, lime, chalk, bolus, loess,
clay, dolomite, diatomaceous earth, calcium and magnesium sulfate,
magnesium oxide, ground plastic materials, as well as fertilizers
such as ammonium sulfate, ammonium phosphate, ammonium nitrate,
urea and plant products such as cereal flour, tree bark powder,
wood powder and nutshell powder, cellulose powder or other solid
carriers.
[0025] The formulations generally contain one of the compounds I or
II or of the mixture of the compounds I and II in a concentration
from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight.
The active ingredients are present in a purity from 90% to 100%,
preferably 95% to 100%, determined by an NMR or HPLC spectrum.
[0026] The application can be carried out before and/or after the
attack by the harmful fungi.
[0027] The active ingredients as such or their formulations can
also be applied as a mixture, i.e. simultaneously, before or
afterwards in conjunction with further fungicides, bactericides,
acaricides, nematicides, insecticides and/or additional active
ingredients, such as herbicides, and/or with fertilizers and/or
growth regulators. When using the active ingredient combination
according to the invention, the application rates may be varied
over a relatively wide range depending on the type of application.
When treating plant parts, the application rates of the active
ingredient combination are generally between 4 and 2000 ppm,
preferably between 8 and 500 ppm.
[0028] The active ingredient compositions and formulations
according to the invention are particularly important for fighting
a variety of fungi on various crops such as barley, wheat, oats,
rye, corn, rice, cotton, vegetable plants such as cucumbers, beans,
tomatoes, potatoes and pumpkin plants, as well as bananas, coffee,
fruit plants soy, vines, ornamental plants or sugar cane.
[0029] The active ingredient compositions and formulations
according to the invention are particularly suitable for fighting
the following phytopathogenic fungi or pathogens: Erysiphe graminis
(powdery mildew) on cereal, Erysiphe cichoracearum and Sphaerotheca
fuliginea on cucurbits, Podosphaera leucotricha on apples, Uncinula
necator on vines, Puccinia species on cereal and soy, Rhizoctonia
species on cotton, rice and lawns, Ustilago species on grain and
sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium
species on cereal, Septoria nodorum on wheat, Botrytis cinerea
(gray mold) on strawberries, vegetables, ornamentals and vines,
Cercospora arachidicola on peanuts, Pseudocercosporella
herpotrichoides on wheat and barley, Pyricularia oryzae on rice,
Phytophthora infestans on potatoes and tomatoes, Phytophthora
capsici on tomatoes or paprika, Plasmopara viticola on vines,
Pseudocercosporella typologies in hops and cucumbers, Alternaria
typologies on vegetables and fruit, Mycosphaerella species in
bananas, Sclerotinia sclerotiorum on oilseed rape and vegetables,
and Fusarium--and Verticillium species on various crops.
[0030] Further details, features and advantages of embodiments of
the invention can be inferred from the following description of
exemplary embodiments with reference to the accompanying drawings,
which show in:
[0031] FIG. 1 the known general structural formula of
flavan-3-ols,
[0032] FIG. 2 the known structural formula of procyanidin B2,
[0033] FIG. 3 the known structural formula of procyanidin B5,
[0034] FIG. 4 the known structural formula of procyanidin A1,
[0035] FIG. 5 the known basic structural formula of stilbenes as
trans-isomer and as cis-isomer,
[0036] FIG. 6 examples of known stilbene derivatives,
[0037] FIG. 7 a graphical representation of fungicidal efficacy of
a mixture of rhaponticin and procyanidin B2,
[0038] FIG. 8 a graphical representation of the fungicidal efficacy
of a mixture of epigallocatechingallate and resveratrol,
[0039] FIG. 9 a graphical representation of the fungicidal efficacy
of a mixture of epigallocatechingallate and
trihydroxy-stilbenglucoside, and
[0040] FIG. 10 a graphical representation of the fungicidal
efficacy of a mixture of gallocatechin and epigallocatechin
gallate.
[0041] Flavan-3-ols are compounds with the known basic structure
shown in FIG. 1. Examples of important representatives of these
compounds are listed below with the corresponding association
R.sup.1 and R.sup.2 of the structural formula:
[0042] R.sup.1.dbd.H; R.sup.2.dbd.H: afzelechin
[0043] R.sup.1.dbd.H; R.sup.2.dbd.H: epiafzelechin
[0044] R.sup.1.dbd.OH; R.sup.2.dbd.H: catechin
[0045] R.sup.1.dbd.OH; R.sup.2.dbd.H: epicatechin
[0046] R.sup.1.dbd.OH; R.sup.2.dbd.OH: gallocatechin
[0047] R.sup.1.dbd.OH; R.sup.2.dbd.OH: epigallocatechin
[0048] Proanthocyanidins are compounds composed of linked
flavan-3-ol moieties. Various types of links are shown below. A
representative of the proanthocyanidins
epicatechin-(4.beta..fwdarw.8)-epicatechin referred to as
procyanidin B2, shown in FIG. 2. Other proanthocyanidins are the
compound epicatechin (4.beta..fwdarw.6)-epicatechin referred to as
procyanidin B5 having the structural formula shown in FIG. 3, and
epicatechin (4.beta..fwdarw.8,2.beta..fwdarw.7) catechin referred
to as procyanidin A1 with the structural formula shown in FIG.
4.
[0049] FIG. 5 shows the basic structural formula of stilbenes as
trans-isomer and a cis-isomer. Table 1 lists the corresponding
radicals R1 to R6 for different stilbenes.
TABLE-US-00001 TABLE 1 Stilbene R1 R2 R 3 R4 R5 R6 Resveratrol OH H
OH H OH H Piceid = 3,5,4'-trihydroxy- glucose H OH H OH H
stilbene-3-O-.beta.-D-glucoside Astringine (3'-OH-piceide) glucose
H OH OH OH H Piceatannol = 3,3',4',5- OH OH H OH H OH
tetrahydroxystilbene Pterostilbene OCH.sub.3 H OCH.sub.3 H OH H
Resveratroloside OH H OH H glucose H
[0050] Table 2 lists the radicals R1, R2 and R3 for various
stilbene derivatives.
TABLE-US-00002 TABLE 2 R1 R2 R3 Name of the compound at C-3 at C-4'
at C-3' 3,5,4'-trihydroxy stilbene-4'- H glucose H
O-.beta.-D-glucoside 3,5,4'-trihydroxy stilbene-4'- H 6-O- H
O-.beta.-D-(6''-O-galloyl) glucoside galloylglucose
Rhapontigenin-3'-O-.beta.-D- H CH.sub.3 O- glucopyranoside glucose
Rhaponticin-6''-O-gallate 6-O- CH.sub.3 OH galloyl- glucose
Rhaponticin-2''-O-gallate 2-O- CH.sub.3 OH galloyl- glucose
Rhaponticin-2''-O-coumarate 2-O- CH.sub.3 OH coumaroyl glucose
Piceatannol-3-O-.beta.-D- glucose H OH glucopyranoside
Piceatannol-3'-O-..beta..-D- H H O- glucopyranoside glucose
Piceatannol-3'-O-..beta..-D- H H O-xylose xylopyranoside
Piceatannol-3'-O-..beta..-D-(6''-O- H H O-(6- galloyl)
glucopyranoside galloyl)- glucose Deoxyrhaponticin-6''-O-gallate
6-O- CH.sub.3 H galloyl- glucose 3,4',5-trihydroxy-stilbene-4'- H
6- H O-.beta.-D-(6''-O-galloyl) glucoside galloylglucose
[0051] Table 3 shows the corresponding radicals R1, R2 and R3 for
the stilbene rhaponticin and for rhaponticin derivatives.
TABLE-US-00003 TABLE 3 R1 R2 Name of the compound at C-3 at C-4'
Rhaponticin glucose CH.sub.3 Rhapontigenin H CH.sub.3
Deoxyrhaponticin glucose CH.sub.3 Deoxyrhapontigenin H CH.sub.3
Dioxyrhaponticin glucose OH
[0052] FIG. 6 shows the structural formulas of the resveratrol
dimers e-Viniferin and d-Viniferin as examples of stilbene
derivatives.
[0053] Material and Methods
[0054] Barley plants (3 plants/container) were cultivated for three
weeks in Frustrorf soil. The inoculation of the leaves with mildew
took place 2 hours after application of the test preparations
(protective application). Fresh conidia of Blumeria graminis f. sp.
hordei were used for the inoculation, species A6, and carried onto
the leaves in the mildew tower by way of wind distribution. For a
leaf segment test, 10 cm long leaf segments, starting from the
stalk base, were cut off and 15 leaves of the youngest as well as
the second youngest leaf were laid out on benzimidazole agar. The
benzimidazole agar consists of 0.5% agar and an admixture of 40 ppm
benzimidazole in one liter of water.
[0055] The concentration of the standard substances for the leaf
application was adjusted to 125, 62.5, 32, 16 and 8 ppm. An
adjuvant was added to the standard substances with BT S240 (50
ml/ha) in order to ensure a uniform distribution of the application
solution on the leaf. The mildew effect was evaluated by counting
the mildew blisters per leaf on a 7 cm long leaf.
[0056] The beneficial fungicidal action of the active ingredient
combination according to the invention is evident from the
following examples. While the individual active ingredients in the
fungicidal action show weaknesses, the combinations of two active
ingredients exhibit an efficacy that exceed the efficacy attained
by simply adding the individual efficacy.
[0057] A synergistic effect is always present in
fungicides/antifungal compounds when the fungicidal action of the
active ingredient combination is greater than the sum of the
individual efficacies.
[0058] The expected efficacy for a given combination of two or
three active ingredients can be calculated according to S. R. Colby
("Calculating Synergistic and Antagonistic Responses of Herbicide
Combinations", Weeds 1967, 15, 20-22) as follows:
E 1 = X + Y - X - Y 100 , ##EQU00001##
[0059] or when using three active ingredients
E 2 = X + Y + Z - X - Y - Z 100 , ##EQU00002##
Note that it wrongly says E1 in the PCT and DE text.
[0060] wherein
[0061] X represents the efficacy when using the active compound A
in an application rate of mg/ha,
[0062] Y represents the efficacy when using the active compound B
in an application rate of mg/ha,
[0063] Z represents the efficacy when using the active compound C
in an application rate of mg/ha,
[0064] E1 represents the efficacy when using the active ingredients
A and B in application rates of m and n g/ha, and
[0065] E2 represents the efficacy when using the active ingredients
A and B and C in application rates of m, n and r g/ha.
[0066] The results of the efficacy against barley powdery mildew
(Blumeria graminis f. sp. Hordei) show a synergistic effect at
certain mixing ratios, as seen in the following tables. In Table 1,
the efficacies calculated for mixtures of the stilbene glucoside
rhaponticin (RHAP) as a stilbene derivative and procyanidin B2
(PROCY) based on the known efficacy of the individual substances
are compared with the observed efficacies. The
concentration-dependent efficacies for the individual substances
and the mixtures are shown graphically in FIG. 7. In this example
and in the following examples, the reference quantity 100 for the
efficacy is the efficacy achieved with a concentration of 125 ppm
of the respective pure substance. Table 4 and FIG. 7 demonstrate
that a synergistic effect, as described above, could be observed at
all the used mixture ratios. This means that when using the
mixtures, the calculated efficacies of the individual substances
are exceeded.
TABLE-US-00004 TABLE 4 Observed Calculated Example Mixture
according to the invention efficacy efficacy 1 Control (untreated)
(100% 0 infection) 2 RHAP + PROCY (16 + 16 ppm) 100 96 3 RHAP +
PROCY (8 + 8 ppm) 72 45 4 RHAP + PROCY (32 + 16 ppm) 100 98 5 RHAP
+ PROCY (16 + 8 ppm) 98 90 6 RHAP + PROCY (16 + 32 ppm) 100 97 7
RHAP + PROCY (8 + 16 ppm) 86 91 8 RHAP + PROCY (62.5 + 16 ppm) 100
98 9 RHAP + PROCY (16 + 62.5 ppm) 100 97 10 RHAP + PROCY (8 + 32
ppm) 100 92
[0067] In Table 5, the efficacies calculated for mixtures of
epigallocatechin gallate (EPIC-G) as flavan-3-ol and resveratrol
(RESV) as stilbene with the systematic designation
trans-3,5,4'-trihydroxystilbene are compared with the observed
efficacies. The concentration-dependent efficacies for the used
individual substances and for the mixtures are shown graphically in
FIG. 8. Table 5 and FIG. 8 show that a synergistic effect, as
described above, could be observed at all the used mixture ratios.
This means that the calculated efficacies are always exceeded when
the mixtures are used.
TABLE-US-00005 TABLE 5 Observed Calculated Example Mixture
according to the invention efficacy efficacy 1 Control (untreated)
(100% 0 infection) 2 EPIC-G + RESV (16 + 16 ppm) 100 91 3 EPIC-G +
RESV (8 + 8 ppm) 100 71 4 EPIC-G + RESV (32 + 16 ppm) 100 97 5
EPIC-G + RESV (16 + 8 ppm) 100 87 6 EPIC-G + RESV (16 + 32 ppm) 100
94 7 EPIC-G + RESV (8 + 16 ppm) 93 80 8 EPIC-G + RESV (62.5 + 16
ppm) 100 98 9 EPIC-G + RESV (16 + 62.5 ppm) 100 92 10 EPIC-G + RESV
(8 + 32 ppm) 100 87
[0068] In Table 6, the efficacies calculated for mixtures of
epigallocatechin gallate (EPIC-G) as flavan-3-ol and
trihydroxystilbenglucoside (TH-STIB-GI) as stilbene are compared
with the observed efficacies. The concentration-dependent
efficacies for the used individual substances and for the mixtures
are shown graphically in FIG. 9. Table 6 and FIG. 9 show that that
a synergistic effect, as described above, could be observed at all
the used mixture ratios.
TABLE-US-00006 TABLE 6 Observed Calculated Example Mixture
according to the invention efficacy efficacy 1 Control (untreated)
(100% 0 infection) 2 TH-STIB-GI + EPIC-G (16 + 16 ppm) 73 56 3
TH-STIB-GI + EPIC-G (8 + 8 ppm) 65 45 4 TH-STIB-GI + EPIC-G (32 +
16 ppm) 92 77 5 TH-STIB-GI + EPIC-G (16 + 8 ppm) 83 67 6 TH-STIB-GI
+ EPIC-G (16 + 32 ppm) 83 60 7 TH-STIB-GI + EPIC-G (8 + 16 ppm) 66
54 8 TH-STIB-GI + EPIC-G (62.5 + 16 ppm) 96 80 9 TH-STIB-GI +
EPIC-G (16 + 62.5 ppm) 92 69 10 TH-STIB-GI + EPIC-G (8 + 32 ppm) 81
74
[0069] In Table 7, the efficacies calculated for mixtures of
gallocatechin (GAL-C) as flavan-3-ol and epigallocatechin gallate
(EPIC-G) as additional flavan-3-ol are compared with the observed
efficacies. The concentration-dependent efficacies for the used
individual substances and for the mixtures are shown graphically in
FIG. 10. Table 7 and FIG. 10 show that a synergistic effect, as
described above, could be observed at ail the used mixture
ratios.
TABLE-US-00007 TABLE 7 Observed Calculated Example Mixture
according to the invention efficacy efficacy 1 Control (untreated)
(100% 0 infection) 2 GAL-C + EPIC-G (16 + 16 ppm) 95 76 3 GAL-C +
EPIC-G (8 + 8 ppm) 97 62 4 GAL-C + EPIC-G (32 + 16 ppm) 99 88 5
GAL-C + EPIC-G (16 + 8 ppm) 100 69 6 GAL-C + EPIC-G + (16 + 32 ppm)
94 78 7 GAL-C + EPIC-G + (8 + 16 ppm) 90 70 8 GAL-C + EPIC-G +
(62.5 + 16 ppm) 100 93 9 GAL-C + EPIC-G + (16 + 62.5 ppm) 95 88 10
GAL-C + EPIC-G + (8 + 32 ppm) 90 72
[0070] The excellent fungicidal efficacy of the active ingredient
combination of the invention against oat crown rust (Puccinia
coronata) is evident from the following examples. While the
individual active ingredients have weaknesses in their fungicidal
efficacy, the respective combinations show an efficacy that exceeds
that of a simple addition of the individual efficacies. The results
of the efficacy against oat crown rust (Puccinia coronata) show a
synergistic effect at certain mixing ratios, as shown in the
following tables.
[0071] Rhaponticin (=RHAP) and procyanidin B2 (=PROCY) and
epigallocatechin gallate (=EPIC-G) and resveratrol (=RESV) were
also tested against oat crown rust (Puccinia coronata) in different
concentrations, see Table 8 and Table 9. Oats were cultivated for
three weeks in Frustrorfer soil. An adjuvant of BT S240 was added
to the standard substances (50 ml/ha) to ensure a uniform
distribution of the application solution on the leaf. The leaves
were inoculated with oat crown rust 8 hours after application of
the standard substances (protective application). For the
application, uredo spores of oat crown rust (Puccinia coronata)
were taken up by a medium which consisted of a mixture of methyl
nonafluoroisobutyl ether and methyl nonafluorobutyl ether. With
this mixture, the medium evaporates very quickly after application
to the leaves, and the rust spores previously distributed with the
medium remain on the leaf surface. After this medium was applied,
the plants were incubated in the dark for 24 h and then laid out in
the leaf segment test. For a leaf segment test, 10 cm long leaf
segments, starting from the stalk base, were cut off and 15 leaves
of the youngest as well as the second youngest leaf were laid out
on benzimidazol agar (0.5% agar, admixture of 40 ppm benzimidazole
after autoclaving). The efficacy against oat crown rust was
evaluated by counting the rust blisters per leaf on a 7 cm long
leaf. The classification took place after 20 DAT (days after
treatment). The synergistic effect was again calculated according
to the Colby formula.
[0072] Oat crown rust (Puccinia coronata) was chosen as a model for
examining the synergistic effect against rust diseases to show that
the compounds of the invention are capable of synergistically
attacking also rust diseases in addition to mildew diseases. Major
rust diseases include, among others, major rust diseases in cereal
such as yellow rust (Puccinia striiformis), brown rust (Puccinia
recondita), leaf rust (Puccinia hordei) or black rust (Puccinia
graminis). Important other rust diseases are found in soy
(Phakopsora pachyrhizi) or in roses, pears, turf grasses.
TABLE-US-00008 TABLE 8 Mixture according Observed Calculated
Example to the invention efficacy efficacy 1 Control (untreated)
(100% 0 infection) 2 RHAP + PROCY 86 74 (62.5 + 62.5 ppm) 3 RHAP +
PROCY 75 62 (32 + 32 ppm) 4 RHAP + PROCY 64 45 (16 + 16 ppm) 5 RHAP
+ PROCY 84 70 (62.5 + 32 ppm) 6 RHAP + PROCY 73 52 (32 + 16 ppm) 7
RHAP + PROCY 81 68 (32 + 62.5 ppm) 8 RHAP + PROCY 73 58 (16 + 32
ppm) 9 RHAP + PROCY 90 77 (125 + 32 ppm) 10 RHAP + PROCY 87 73 (32
+ 125 ppm) 11 RHAP + PROCY 77 63 (16 + 62.5 ppm)
TABLE-US-00009 TABLE 9 Mixture according Observed Calculated
Example to the invention efficacy efficacy 1 Control (untreated)
(100% 0 infection) 2 EPIC-G + RESV 96 86 (62.5 + 62.5 ppm) 3 EPIC-G
+ RESV 92 78 (32 + 32 ppm) 4 EPIC-G + RESV 72 54 (16 + 16 ppm) 5
EPIC-G + RESV 92 84 (62.5 + 32 ppm) 6 EPIC-G + RESV 83 71 (32 + 16
ppm) 7 EPIC-G + RESV 93 81 (32 + 62.5 ppm) 8 EPIC-G + RESV 84 72
(62.5 + 16 ppm) 9 EPIC-G + RESV 83 69 (16 + 62.5 ppm)
LIST OF ABBREVIATIONS
[0073] EPIC-G Epigallocatechin gallate [0074] GAL-C Gallocatechin
[0075] PROCY Procyanidine [0076] RESV Resveratrol (trans-3,5
4'-trihydroxystilbene) [0077] RHAP Rhaponticin [0078] TH-STIB-GI
Trihydroxystilbenglucoside:
3,4',5-trihydroxystilbene-3-O-beta-D-glucopyranoside
* * * * *